CN114174312A - Air-stable Ni (0) -olefin complexes and their use as catalysts or precatalysts - Google Patents

Air-stable Ni (0) -olefin complexes and their use as catalysts or precatalysts Download PDF

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CN114174312A
CN114174312A CN202080053726.5A CN202080053726A CN114174312A CN 114174312 A CN114174312 A CN 114174312A CN 202080053726 A CN202080053726 A CN 202080053726A CN 114174312 A CN114174312 A CN 114174312A
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same
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J·科尔奈拉
L·纳特曼
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Studiengesellschaft Kohle gGmbH
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Studiengesellschaft Kohle gGmbH
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Abstract

The invention relates to air-stable, binary Ni (0) -olefin complexes and to the use thereof in organic synthesis.

Description

Air-stable Ni (0) -olefin complexes and their use as catalysts or precatalysts
The invention relates to air-stable binary Ni (0) -olefin complexes and their use for organic synthesis.
In recent years, nickel (Ni) catalysis has become an increasingly and powerful area of research due to new branching and reactivity patterns for organic synthesis. In these efforts, Ni (0) -olefin complexes have become an effective Ni (0) source due to their high affinity for ligand exchange. Such as Ni (COD)2Bis (cyclooctadiene) Ni (0)) has become the basic Ni (0) source for the development of new catalytic reactivity.
However, binary Ni (0) complexes with only olefins as ligands suffer from large instability and rapid decomposition problems when exposed to air, which therefore limits its operation to Schlenk techniques or glove boxes under inert atmosphere.
In the 1960 s, DE 1191375 AS disclosed AS olefin and Ni saltTo synthesize a first binary metal-olefin complex. After this publication, Ni (0) -olefin compounds, in particular Ni (COD)2Have served as precatalysts to exhibit multiple transitions that affect various aspects of chemical science. Furthermore, Ni (COD)2And all-trans-ni (cdt) have served as catalysts for different important industrial processes occurring on the ton scale, i.e. the polymerization and cyclotrimerization of olefinic compounds.
However, in the case of homogeneous catalysis, Ni (COD)2Has become the primary, if not the only, source of Ni (0) for reaction discovery (fig. 1 a). Sure, Ni (COD)2Is commercially available due to its remarkable stability at low temperature under an inert atmosphere. Ni (COD)2The instability of the olefinic ligands in (b) when competing with more nucleophilic counterparts such as phosphines, diamines or carbenes has placed this compound at the front of the reaction findings and is therefore clearly advantageous in a variety of catalytic conversions.
However, although it has important properties, Ni (COD) is used2Is associated with its high instability and immediate decomposition upon exposure to air, which results in tedious manipulation and requires the use of glove box or Schlenk techniques. Alternative binary Ni (0) -olefin complexes are limited to Ni (CDT) (cis or trans), Ni (COT)2Or Ni (C)2H4)3It is even more unstable and extremely air sensitive (fig. 1 a).
For these reasons, chemists have cumin for many years in an attempt to study alternative Ni (0) precursors, which are stable in air, recognizing that such precatalysts would allow the development of a facile and highly practical process from the point of view of preparation time and reaction facilities.
Indeed, the unique properties and reactivity of Ni (0) -olefin complexes remain paramount, and chemists have made great efforts to manipulate such compounds under aerobic conditions, such as developing other Ni (ii) pre-catalysts (fig. 1b) or paraffin capsules (paraffin capsules) which allow the use of Ni (cod) in bench-top facilities2) What is needed isAs an example.
However, there is still a need to provide a practical solution for using air stable Ni (0) precursors.
The present inventors have developed a unique set of compounds such as those made of Ni (I)Xstb)3The synthesis of the illustrated 16-electron binary Ni (0) -stilbene complexes and their catalytic activity was investigated, wherein X describes different substitution patterns.
In contrast to all reported 16-and 18-electron Ni (0) -olefin complexes, Ni: (Xstb)3When stored in a refrigerator at-18 ℃, was stable in air for several months without significant decomposition. The complexes can be manipulated without the use of a glovebox or Schlenk and are highly modular, thus allowing ligand exchange with many commonly used ligands in Ni catalysis, such as diamines, phosphines, N-heterocyclic carbenes (NHCs), etc., providing well-defined Ni (0) -L species. In addition, their catalytic activity is Ni (COD)2Are benchmark and have been shown to be excellent precursors for a wide variety of different Ni-catalyzed reactions.
The present invention therefore relates to Ni (R)3-a complex, wherein Ni represents Ni (0) and R may be the same or different, and represents a trans stilbene of formula (I):
Figure BDA0003487304920000031
wherein R is1-R10May be the same or different and is selected from H, Cl, Br, F, CN, C1-C8Alkyl or C3-C6Cycloalkyl, which alkyl or cycloalkyl may optionally be substituted with one or more halogen,
wherein R is11-R12May be the same or different, and is selected from H, C1-C8Alkyl radical, C3-C6Cycloalkyl, -O-C1-C8Alkyl or-O-C3-C6A cycloalkyl group,
provided that R is1-R12Is not hydrogen.
Ni (R) of the present invention shown in the context of the present invention3In the complex, Ni represents Ni (0).
In the present invention, Ni (R)3In another embodiment of the complex, R are identical or different, and in formula (I), R is1-R5And R6-R10Is the same or different and is selected from the group consisting of Cl, Br, F, CN, C1-C8Alkyl or C3-C6Cycloalkyl, which alkyl or cycloalkyl may optionally be substituted with one or more halogen, preferably selected from C1-C8Alkyl, which may optionally be branched and/or substituted with one or more halogens, and other R1-R10Is hydrogen, and R11-R12May be the same or different, and is selected from H, C1-C8Alkyl radical, C3-C6Cycloalkyl, -O-C1-C8Alkyl or-O-C3-C6A cycloalkyl group.
In the present invention, Ni (R)3In yet another embodiment of the complex, R are the same or different, and in formula (I), R is3And R8Are identical or different and are selected from C1-C8Alkyl, which alkyl or cycloalkyl may optionally be substituted with one or more halogens, and other R1-R10Is hydrogen, and R11-R12May be the same or different, and is selected from H, C1-C8Alkyl radical, C3-C6Cycloalkyl, -O-C1-C8Alkyl or-O-C3-C6A cycloalkyl group.
In the present invention, Ni (R)3In another embodiment of the complex, R are identical or different, and in formula (I), R is3And R8Are identical or different and are selected from branched C3-C8Alkyl radicals such as the isopropyl, tert-butyl, neopentyl, which may optionally be substituted by one or more halogens, and further R1-R10Is hydrogen, and R11-R12May be the same or different, and is selected from H, C1-C8Alkyl radical, C3-C6Cycloalkyl, -O-C1-C8Alkyl or-O-C3-C6A cycloalkyl group.
In the present invention, Ni (R)3In yet another embodiment of the complex, R are the same, and in formula (I), R is3And R8Are identical or different and are selected from C1-C8Perfluoroalkyl, and other R1-R10Is hydrogen, and R11-R12May be the same or different, and is selected from H, C1-C8Alkyl radical, C3-C6Cycloalkyl, -O-C1-C8Alkyl or-O-C3-C6A cycloalkyl group.
In the present invention, Ni (R)3In yet another embodiment of the complex, R are the same, and in formula (I), R is3And R8Each is C1-C8Perfluoroalkyl, preferably CF3And other R1-R10And R11-R12Is hydrogen.
In the present invention, alkyl is intended to mean any alkyl group having from 1 to 8 carbon atoms, including branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl.
In the present invention, cycloalkyl is intended to mean any cycloalkyl group having 3 to 6 carbon atoms, including alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and substituted alkyl rings.
Each alkyl or cycloalkyl group may be substituted with one or more halogens, particularly fluorine.
The invention also relates to a process for preparing the air-stable Ni (R) of the invention3-a complex, wherein Ni represents Ni (0) and R may be the same or different, and represents a trans stilbene of formula (I):
Figure BDA0003487304920000041
wherein R is1-R10May be the same or different and is selected from the group consisting of H, Cl, Br, F, CN, C1-C6Alkyl or C3-C6Cycloalkyl, which alkyl or cycloalkyl may optionally be substituted with one or more halogen,
wherein R is11-R12May be the same or different, and is selected from H, C1-C6Alkyl radical, C3-C6Cycloalkyl, -O-C1-C6Alkyl, or-O-C3-C6A cycloalkyl group,
wherein is selected from NiF2、NiCl2、NiBr2、NiI2、Ni(OTf)2、Ni(BF4)2、Ni(OTs)2Ni (glyme) Cl2Ni (glyme) Br2Ni (diglyme) Cl2Ni (diglyme) Br2、Ni(NO3)2、Ni(OR13)2(wherein R is13represents-C (O) -C1-C6Alkyl, optionally substituted with one or more halogens, preferably Cl or F, (acetyl acetonate)2Ni、Ni(Ac)2Or mixtures thereof, in the presence of a nickel (II) compound of the formula Al (R)14)3With trans stilbene of the formula (I), preferably with at least 3 equivalents, preferably at least 2 equivalents, of trans stilbene of the formula (I), in the presence of an aluminum alkyl of (A), where R is14May be the same or different, and is selected from C1-C6Alkyl or C3-C6A cycloalkyl group.
Preparation of air-Stable Ni (R) in accordance with the invention described above3In one embodiment of the complex, the formula Al (R)14)3The aluminum alkyl is selected from Al (CH)3)3Or Al (C)2H5)3。
Preparation of air-Stable Ni (R) in accordance with the invention described above3-in still another embodiment of the complex, R represents claim 2-5 trans stilbene of formula (I) as defined in any of the definitions.
In a further embodiment of the process according to the invention, trans-stilbenes of the formula (I) are used, where R is1-R12Is not hydrogen.
In the process of the present invention, the choice of solvent is not critical as long as the solvent is an aprotic non-polar organic solvent selected from diethyl ether, aromatic solvents such as benzene, toluene, aliphatic hydrocarbon solvents having 5 to 8 carbon atoms such as pentane, hexane or mixtures thereof. The reaction conditions are also not critical and the reaction is generally carried out at a temperature of from-78 ℃ to 0 ℃, preferably from-30 ℃ to-5 ℃, at ambient pressure and optionally under an inert atmosphere. The reaction is generally carried out with a slight stoichiometric excess of trans stilbene of formula (I) (preferably at least 3 equivalents) and Al (R)14)3Preferably at least 2 equivalents, of trans stilbene of the formula (I) and Al (R)14)3Preferably up to an additional 10 mol%.
The invention also relates to the air-stable Ni (R) of the invention3-use of a complex as a catalyst in organic synthesis, wherein:
ni represents Ni (0), and R may be the same or different, and represents a trans stilbene of formula (I):
Figure BDA0003487304920000061
wherein R is1-R10May be the same or different and is selected from the group consisting of H, Cl, Br, F, CN, C1-C6Alkyl radical, C3-C6Cycloalkyl, which alkyl or cycloalkyl may optionally be substituted with one or more halogen, and
R11-R12may be the same or different, and is selected from H, C1-C8Alkyl radical, C3-C6Cycloalkyl, -O-C1-C6Alkyl or-O-C3-C6A cycloalkyl group,
optionally, provided that R1-R12Is not hydrogen.
Catalytic performance
Having demonstrated the ability to exchange ligands with commonly used ligands in Ni catalysis, the present inventors have begun to develop the catalytic performance of the Ni (0) -olefin complexes of the present invention as a Ni (0) source in a number of related organic transformations. To this end, the inventors have based their catalysts on the Ni (0) source in the various Ni-catalyzed transformations and compared the properties of the Ni (0) -olefin complexes of the invention with Ni (COD)2And some ni (ii) precatalyst. The catalytic performance is achieved by using a catalyst (Ni (0) (4-CF3stb)3) And (Ni (0) ()4-tBustb)3) Are exemplary developed.
The inventors initially developed the feasibility of catalyzing Suzuki couplings due to its great importance in modern syntheses. The use of the Ni (0) -olefin complex of the present invention as a precatalyst allows the heteroaryl boronic acid and heteroaryl bromide to be coupled in excellent yields (fig. 4a. > 99%).
Another reaction of high interest is the oxidative cycloaddition reported by Ogoshi between a nitrile and a diene. Although the reaction uses a higher temperature (130 ℃), the Ni (0) -olefin complex of the present invention demonstrates a stable and catalytic ability, which provides the product in 84% yield (fig. 4 b).
More recently, C-H activation strategies based on Ni catalysis have emerged, which use Ni (0) as the pre-catalyst source. As an example, Chatani demonstrated the synthesis of isoquinolinones (isoquinolones) from simple amides and alkynes. Simple PPh3Are reported to be the best ligands for such purposes; in this case, the Ni (0) -olefin complexes of the present invention also appear to be excellent candidates as Ni (0) source, providing excellent yields (fig. 4 c.94%).
To further test the ability of the Ni (0) -olefin complexes of the present invention to act as catalysts, the present inventors adjusted their focus to the formation of important C — N bonds. To this end, the inventors have utilized reports of amination of aryl halides with both aromatic and aliphatic amines. When SIPr is used as a ligand, the N of the present inventionThe i (0) -olefin complex smoothly provided excellent yields of product (fig. 4 d.91%). When aromatic amines were used instead, dppf was used as ligand and a smooth conversion to bis-aromatic amines was obtained (fig. 4 e.90% yield). It is worth noting that in this latter case some Ni-complexes require somewhat higher temperatures than reported, presumably due to (dppf) Ni (0) (4-CF3stb) high stability of the intermediate (FIG. 3), hence with its Ni (COD)2The analogues require higher energy to promote dissociation of the stilbene ligand than does the analogue.
Activation of acetals for arylation has recently been reported by Doyle. Despite the presence of protic solvents such astAmOH, but the Ni (0) -olefin complex of the present invention proved to be an excellent candidate, which resulted in excellent arylation yields (fig. 4 f.85%). The ability of low-valent Ni species to activate amides through its C — N bond has been demonstrated to be a powerful cleavage for organic synthesis. The Ni (0) -olefin complex of the present invention is distinguished in this context by the formation of an ester from N-Me-Boc amide and tryptophol in high yield (fig. 4 g.65%). The Ni (0) -olefin complexes of the present invention also exhibit an excellent Ni (0) source in the powerful alkyl-alkyl Negishi cross-coupling, as exemplified by the 58% yield of C — C bond obtained in fig. 4 h. It is worth mentioning that these last two reactions were successfully performed using terpyridine and PyBOX derivatives as ligands, thus highlighting the ease of conversion of the Ni (0) -olefin complexes of the present invention to active L-Ni (0) species with tridentate ligands.
The Negishi cross-coupling between the aryl bromide and the vinyl zinc reagent catalyzed by the Ni (0) -olefin complex 2 of the present invention enables similar yields (92%, fig. 4i) to be achieved compared to the corresponding Ni (0) precursor reported. Ni (0) -olefin complexes have also been used as precursors for the production of heterogeneous Ni (0) particles without the addition of ancillary ligands. In this context, the Ni (0) -olefin complexes of the present invention have proven to be excellent candidates as shown in the reduction of thiomethyl ethers with silanes (91%, fig. 4 j).
Recently, highly electron donating ligands such as NHC and Ni (COD) were used2The phase combination has become via C-HSelection of the catalytic system in the case of an activated hydroarylation strategy. However, it has been noted that this specific combination of catalyst and ligand leads to the formation of undesirable Ni pi-allyl complexes as a result of the hydrometallation of COD ligands. Structural evidence and reactivity studies have led to the conclusion that such substances prevent catalytic activity and turnover (turnover). The inventors expect that the Ni (0) -olefin complexes of the present invention can avoid the deleterious pathways observed in certain C-H arylation strategies and thus favor productive catalysis. To test this hypothesis, the inventors examined the direct hydroarylation of alkynes using electron deficient aromatics. As reported, Ni (COD)2Use in combination with IMes provides trace amounts of hydroarylation products. On the other hand, the Ni (0) -olefin complex 2 using the present invention smoothly reacts at room temperature, and a significant 90% yield of the product is obtained (fig. 5). This result highlights the fact that the Ni (0) -olefin complex of the present invention can act as a Ni (0) precatalyst and, in some cases, it can serve as a unique candidate when COD side reactions occur. It is important to mention that the use of the Ni (0) -olefin complexes of the present invention does not require the use of highly sensitive free carbenes, and simply using a combination of the parent HCl salt with a base is sufficient to achieve reactivity.
It is important to mention that in all the examples in which the Ni (0) -olefin complexes of the invention are precatalysts, the reaction facilities are carried out in an open air environment and in a bench (bench). Thus, the use of the glove box is dictated by the sensitivity of the optimal ligand for each particular case and never by the Ni-olefin pre-catalyst. In summary, these results highlight Ni: (Xstb)3(2-6) competitiveness as an effective Ni (0) source in a variety of catalytic situations. Furthermore, the good yields obtained when using the Ni (0) -olefin complexes of the present invention highlight its modularity properties when different chelating or nucleophilic ligands are intended to be used.
The invention is explained in more detail with reference to the figures and the experimental part.
The attached drawings show:
FIG. 1. a: binary Ni (0) olefin complexes of the prior art for Ni catalysis.
b: current strategies to address the air sensitivity problem related to the Ni (0) species;
c: with Ni (Fstb)3The invention exemplified: air-stable 16-electron Ni (0) -olefin complex
d: six different inventive Ni: (Xstb)3Complexes (1-6), each with different aryl substituent(s) on each aryl nucleus, and their preparation and stability.
FIG. 2 Synthesis of complexes 1 and 2:
reaction conditions are as follows: all trans-Ni (CDT) (1.0 equiv.), trans stilbene or trans- (4-trifluoromethylphenyl) stilbene (3.30 and 3.15 equiv., respectively) in THF or Et at-5 deg.C2And (4) in O.
FIG. 3: complex 2 is ligand exchanged with different commonly used ligands in catalysis:
a)2(1.0 equiv.), dppf (1.0 equiv.), in THF at 25 ℃ for quantification;
b)2(1.0 equiv.), bipy (1.0 equiv.), in THF at 25 ℃ for quantification;
c)2(1.0 equiv.), PPh3(2.0 equiv.) in THF at 25 deg.C for quantification;
d)2 slow crystallization in THF at-78 ℃. Ar ═ p-CF3-C6H4。
FIG. 4: 2 catalytic performance in multiple Ni catalyzed transitions.
Suzuki cross-coupling;
b. a cycloisomerization reaction;
c.C-H activation;
Buchwald-Hartwig C-N bond formation using alkylamines;
Buchwald-Hartwig C-N bond formation using arylamines;
f. C-O arylation of acetals;
g. activation of the C-N bond of the amide to form an ester;
h. alkyl-alkyl cross coupling;
negishi cross-coupling;
j. C-SMe reduction with silane.
FIG. 5: complex 2 avoids the traditional COD side reaction.
Fig. 6 shows two industrially relevant transformations and coordination of catalyst 6.
As shown in FIG. 6A, it is also in two industrially relevant transformations (which require prior art Ni (COD))2) The stability and convenience of ligands exchanged with other olefins was demonstrated. As shown in FIG. 6A, 2M3BN (2-methyl-3-butenenitrile (44) — in Ni: (B) (II))4-tBustb)3(6) Ni-catalyzed isomerization to 3PN (3-pentenenitrile, (45) in the presence of butadiene, which is crucial for the efficient synthesis of adiponitrile from butadiene, this conversion being aided by PPh under pure conditions3And provides comparable reactivity levels close to 45 (67%). Another process is Ni catalyzed SHOP (Shell higher olefin process) (fig. 6B), which is capable of oligomerizing ethylene to obtain higher molecular weight alpha-olefins. Complex 6 together with the ligand mixture shown in figure 6B successfully catalyzes the formation of a-olefin mixtures with high efficiency under non-optimized conditions and without pre-catalyst separation. These results highlight the potential of 6 in industrially relevant facilities, thus providing an air and temperature stable alternative to the current Ni (0) catalysts.
Although Ni (b)4-tBustb)3(6) Ni (COD) which can be considered as air-stable2But the underlying coordination chemistry of the two complexes is significantly different. For example, when Ni (COD)2With 4.0 equivalents of PPh3Upon mixing, Ni (PPh) is generally obtained3)4And (PPh)3)2Inseparable mixture of ni (cod) (fig. 6C, top). On the other hand, when 6 is used instead, a complete conversion to the 16-electron compound 45 is formed (fig. 6C, bottom). These differences in coordination chemistry provide an orthogonal tool (an orthogonal tool) for existing strategies for the synthesis of well-defined L-Ni (0) -olefin complexes.
General experimental remarks
Unless otherwise specified, all operations are such thatPerformed in a heat gun dried glassware under dry argon using Schlenk techniques. Ni (A), (B)Xstb)3Stored in a screw cap vial under air in a refrigerator (-18 ℃), except for Ni: (II)4-tBustb)3It is stored on the test stand. All complexes were weighed in air. The anhydrous solvent was distilled from a suitable drying agent and transferred under argon: THF, Et2O (Mg/anthracene), CH2Cl2，CH3CN(CaH2) Hexane, toluene (Na/K), Et3N, DMA, 1, 4-bis
Figure BDA0003487304920000101
Alkane (MS), CPME, NMP andtAmOH was purchased on a moisture free scale and stored on MS. Anhydrous K3PO4，NaOtBu and NaHMDS were stored in a Schlenk or glovebox. Flash column chromatography (Flash column chromatography): merck silica gel 60(40-63 μm). Ms (ei): finnigan MAT 8200(70 eV). Accurate mass determination: MAT 95 (Finnigan). NMR spectra were recorded using a Bruker Avance VIII-300 or Bruker Avance III HD 400MHz spectrometer.1The H NMR spectrum is referenced to the residual protons of the deuterated solvent used.13The C NMR spectrum is D-coupled with an internal reference NMR solvent13C resonance. Chemical shifts (δ) are given in ppm relative to TMS (tetramethylsilane), and coupling constants (J) are given in Hz.19F NMR spectra are externally referenced CFCl3Is/are as follows19F resonates.31P NMR spectra are external reference H3PO4Is/are as follows31P resonates.
General procedure for the preparation of (E) -stilbene
Figure BDA0003487304920000111
The substituted benzaldehyde (1 eq) was added to THF (0.3M) in a three-necked round bottom flask equipped with a large stir bar and reflux condenser. The solution was cooled to-78 ℃ and TiCl was added dropwise4(1.25 equiv.). The reaction is allowed to warm toRoom temperature, and stirred for 10 min. Zn powder (2.5 equivalents) was added in several portions over 2 min. The reaction was refluxed for 3h and then allowed to cool to room temperature. Water (1.5 XTHF amount) was added followed by HCl (0.1 XTHF amount, 3M). The reaction was stirred for 5min and transferred to a separatory funnel. The aqueous layer was extracted with MTBE (2X double amount of THF), the combined organic layers were washed with saturated aqueous NaCl solution and over MgSO4And drying. The solvent was evaporated under reduced pressure, and the residue was subjected to column chromatography. The purified product was dried under high vacuum.
(E) -1, 2-bis (4- (trifluoromethyl) phenyl) ethane
Figure BDA0003487304920000112
According to the general procedure starting from 4-trifluoromethylbenzaldehyde (11.0mL, 14.0g, 80.5mmol), TiCl4(11.0mL, 19.0g, 100.3mmol, 1.25 equiv.) and Zn powder (13.0g, 198mmol, 2.5 equiv.). Column chromatography: gradient hexane: MTBE (100: 0-99: 1).
Yield: 8.44g, 26.7mmol, 66%; colourless solid
(E) -1, 2-bis (4- (tert-butyl) phenyl) ethylene
Figure BDA0003487304920000113
According to the general procedure starting from 4- (tert-butyl) benzaldehyde (10.20ml, 9.86g, 60.8mmol, 1 eq), TiCl4(20.0mL, 34.6g, 182.4mmol, 3 equiv.) and Zn powder (29.8g, 456mmol, 7.5 equiv.). Column chromatography: gradient hexane: MTBE (50: 1-20: 1). Spectroscopic data is according to the literature.
Yield: 3.98g, 13.6mmol, 45%; colourless solid
(E) -1, 2-bis (4-fluorophenyl) ethane
Figure BDA0003487304920000121
According to the general procedure starting from 4-fluorobenzaldehyde (1.30ml, 1.50g, 12.09mmol, 1 eq), TiCl4(1.60mL, 2.75g, 14.50mmol, 1.2 equiv.) and Zn powder (1.98g, 30.22mmol, 2.5 equiv.). Column chromatography: 99: 1 (hexane: MTBE). Spectroscopic data is according to the literature.
Yield: 1.28g, 5.91mmol, 49%; colourless solid
(E) -1, 2-bis (3, 5-dimethylphenyl) ethane
Figure BDA0003487304920000122
According to the general procedure starting from 3, 5-dimethylbenzaldehyde (5.01ml, 5.00g, 37.27mmol, 1 eq), TiCl4(4.90mL, 8.48g, 44.72mmol, 1.2 equiv.) and Zn powder (6.10g, 93.28mmol, 2.5 equiv.). Column chromatography: 50: 1 (hexane: MTBE). Spectroscopic data is according to the literature.
Yield: 2960mg, 18.63mmol, 67%; colourless solid
Synthesis of (E) -1, 2-di-p-tolylethylene
Figure BDA0003487304920000131
4-Methylstyrene (1.98mL, 1.77g, 15mmol, 1 equiv.) and dibasic Grubbs (9.4mg, 0.015mmol, 0.1 mol%) are dissolved in DCM (3 mL). The reaction was refluxed for 3h, the solvent was evaporated under reduced pressure, and the solid was purified by column chromatography (pure hexane). Spectroscopic data is according to the literature.
Yield: 1.1212g, 5.38mmol, 72%; colourless solid
Preparation of Ni (stb)3(1)
Figure BDA0003487304920000132
Ni (CDT) (794mg, 3.60mmol) was added to a Schlenk tube via an argon gas cylinder (CDT ═ 1, 5, 9-trans, trans-cyclododecatriene), and dissolved in THF (7 mL). The solution was filtered under argon into a Schlenk tube maintained at-78 ℃. The filter cake was washed with 3mL of THF. To a separate Schlenk tube was added trans stilbene (2.13g, 11.87mmol, 3.30 equiv.) and a vacuum/argon cycle was performed. The ligand was suspended in THF (10mL) and transferred as a suspension to a first Schlenk tube followed by a wash (2mL THF) to ensure quantitative transfer. The reaction was stirred at-78 ℃ for 10min, then placed in a cooling bath at-5 ℃ and stirred at that temperature for 12 h.
The argon frit (frat) was cooled to-30 ℃ and the reaction was transferred to the frit. The mixture was allowed to cool for 1min and then filtered with positive pressure argon. The solids on the frit were dried by passing a stream of argon through the frit. The solid was then transferred to a Schlenk tube and further dried under high vacuum at room temperature to yield 1 as an air stable, red-brown solid (1.07g, 1.66mmol, 46%).
Preparation of Ni (4-CF3stb)3(2)
Figure BDA0003487304920000141
Ni (CDT) (1, 5, 9-trans, trans-cyclododecatriene) (610mg, 2.76mmol) was added to a Schlenk tube via an argon gas cylinder, and fresh Et at-78 ℃2O (10mL) was added to suspend the starting material. Addition of trans-pCF to a separate Schlenk tube3Stilbene (2.28g, 9.12mmol, 3.15 equiv.) and a vacuum/argon cycle was performed. The ligand was suspended in Et2O (10mL) and transferred as a suspension to a first Schlenk tube followed by several washes (3+2+2mL) to ensure quantitative transfer. The reaction was placed in a cooling bath at-5 ℃ and stirred at that temperature for 3 h.
The argon frit was cooled to-30 ℃ and the reaction was transferred to the frit. The reaction was allowed to cool for 1min and then filtered with positive pressure argon. Et applied to the solid on the glass frit2O (3X 2mL) and by purging with argonAn air stream is passed through the frit for drying. The solid was then transferred to a Schlenk tube and further dried under high vacuum at room temperature to yield 2 as an air stable red solid (1.93g, 1.92mmol, 70%). The catalyst was stored under air in a refrigerator.
From Ni (acac)2Preparation of Ni (4-CF3stb)3
Figure BDA0003487304920000142
Anhydrous Ni (acac) was added to a 100mL Schlenk tube via an argon gas cylinder2(904.4mg, 3.52mmol), and (E) -1, 2-bis (4- (trifluoromethyl) phenyl) ethane (3.50g, 11.1mmol, 3.14 equiv.). Diethyl ether (20mL) was added and the solution was cooled to-20 ℃. Subjecting AlEt3(neat) (1.10mL, 7.5mmol, 2.1 equiv.) was dissolved in diethyl ether (5 mL). Then, this solution was added dropwise over 10min to a solution containing Ni (acac)2And Schlenk of stilbene ligands. The reaction was stirred at-20 ℃ for 1 hour and then cooled in a dry ice bath (-78 ℃) for 10 minutes. The suspension was filtered on a cooled (-78 ℃) argon frit, which left the product on the frit. The solid was washed with diethyl ether (2 × 2mL) and dried under high vacuum. Mixing Ni (A) withFstb)3Isolated as a red solid (2.17g, 2.16mmol, 61%) in pure form. Other Ni (0) -complexes were prepared as described above.
Catalytic reaction
5- (Thien-3-yl) pyrimidine (13)
Figure BDA0003487304920000151
Mixing Ni (A) with4-CF3stb)3(2.0mg, 0.002mmol, 0.005 equiv.), 5-bromopyrimidine (64.5mg, 0.406mmol), thiophen-3-ylboronic acid (102.3mg, 0.800mmol, 2 equiv.), dppf (1.1mg, 0.002mmol, 0.005 equiv.) and anhydrous K3PO4(135mg, 0.64mmol, 1.5 equiv.) in a screw cap vial which is then subjected to a vacuum/argonAnd (5) circulating the gas. Adding 1, 4-bis
Figure BDA0003487304920000153
Alkane (1mL) and the reaction was heated to 80 ℃ for 8 h. Water was added and the aqueous layer was washed with 10mL Et2And extracting for 3 times by using O. The combined organic layers were washed with MgSO4Dried and evaporated under reduced pressure. The crude product was subjected to column chromatography (3: 1-1: 1; hexane: EtOAc) to give a white solid (66.7mg,>99%) of 13 in analytically pure form. When complex 2 samples were stored in a refrigerator>After 100 days, the same yield was obtained when using it as precatalyst.
4, 5-dimethyl-2-phenylpyridine (16)
Figure BDA0003487304920000152
Mixing Ni (A) with4-CF3stb)3(50.4mg, 0.05mmol, 0.1 equiv.) was placed in a pressure-tight Schlenk tube (which was sealed) and subjected to one vacuum/argon cycle. The Schlenk tube was transferred to a glove box and PCy was added3(56.1mg, 0.2mmol, 0.4 equiv.) and the Schlenk was removed from the glove box again. Toluene (3mL) was added followed by 2, 3-dimethylbut-1, 3-diene (226.3. mu.L, 164.3mg, 2mmol, 4 equiv.) and benzonitrile (51.1. mu.L, 51.6mg, 0.5 mmol). The Schlenk tube was sealed pressure tight and heated to 130 ℃ for 48 h. The solvent was removed under reduced pressure and the crude product was purified by column chromatography (9: 1-5: 1; hexane: EtOAc) to give 16(76.7mg, 0.419mmol, 84%) as a yellow oil.
3, 4-dipropyl-2- (pyridin-2-ylmethyl) isoquinolin-1 (2H) -one (19)
Figure BDA0003487304920000161
To a 10-mL pressure-tight Schlenk tube was added N- (pyridin-2-ylmethyl) benzamide (106.1mg, 0.50mmol), PPh3(52.5mg, 0.20mmol, 0.4 equiv.),4-octyne (0.22mL, 1.50mmol, 3.0 equiv.) and Ni (4 -CF3stb)3(50.4mg, 0.05mmol, 0.1 equiv.). Dry toluene (2mL) was added and the reaction mixture was placed in a pre-heated oil bath at 170 ℃ and stirred for 20 h. After cooling to room temperature, the solvent was removed under reduced pressure. Purification of the crude residue by column chromatography (1: 1; hexane: EtOAc) afforded pure 19(151mg, 0.47mmol, 94%) as a yellow oil.
4- (4- (trifluoromethyl) phenyl) morpholine (22)
Figure BDA0003487304920000162
Adding Ni (C) to a 12mL screw cap vial4-CF3stb)3(27.2mg, 0.027mmol, 0.05 equiv.), SIPr. HCl (26.8mg, 0.063mmol, 0.116 equiv.), and dry CPME (1.5 mL). 4-Chlorobenzotrifluoride (72. mu.L, 0.540mmol, 1.00 equiv.) and morpholine (57. mu.L, 0.648mmol, 1.20 equiv.) were added to the solution. While the solution was stirred at room temperature for 15min, the mixture became orange-yellow. NaOtBu (2M THF, 543. mu.L, 1.080mmol, 2.00 equiv.) was then added and the brown reaction mixture was stirred in a pre-heated oil bath at 100 ℃ for 4 h. After cooling to room temperature, the solvent was removed under reduced pressure. Column chromatography of the crude residue (9: 1; hexane: EtOAc) afforded 22(114mg, 0.493mmol, 91% yield) as a colorless solid.
N- (4-methoxyphenyl) -2, 5-dimethylaniline (825)
Figure BDA0003487304920000163
Adding Ni (C) to a 12mL screw cap vial4-CF3stb)3(20.1mg, 0.02mmol, 0.02 equiv.), dppf (22.2mg, 0.04mmol, 0.04 equiv.) and anhydrous sodium tert-butoxide (134.5mg, 1.40mmol, 1.40 equiv.). Toluene (2mL) was added followed by 2-chloro-p-xylene (0.134mL, 1.00mmol, 1.00 equiv.) and p-anisidine (147.8mg, 1.20mmol, 1.20 equiv.). Additional toluene (2mL) was added and the vial was placedIn a preheated oil bath at 130 ℃ and stirred for 48 h. After cooling to room temperature, the reaction mixture was diluted with EtOAc and water was added, and the layers were separated. The aqueous layer was extracted with EtOAc and the combined organic layers were over MgSO4And drying. The solvent was removed under reduced pressure, and the crude residue was purified via column chromatography (gradient: 50: 1-20: 1; hexane: EtOAc) to provide 25(205.1mg, 0.90mmol, 90% yield) as an orange oil.
2- (2- (trifluoromethyl) phenyl) -2H-chromene (28)
Figure BDA0003487304920000171
Adding Ni (C) to a 12mL screw cap vial4-CF3stb)3(58.6mg, 0.05mmol, 0.09 eq.) and PPh3(39.3mg, 0.15mmol, 0.27 equiv.). Adding 1, 4-bis
Figure BDA0003487304920000173
Alkane (1ml) and the solution was stirred for 5 min. To a 50mL Schlenk tube was added 2-ethoxy-2H-chromene (98.9mg, 0.56mmol), (2- (trifluoromethyl) phenyl) boronic acid (189.9mg, 1.00mmol, 1.78 equiv.), bis
Figure BDA0003487304920000174
Alkane (23mL) and t-AmOH (2 mL). The catalyst + ligand solution was transferred to two second Schlenk tubes and the reaction was placed in a pre-heated oil bath at 100 ℃ for 40 min. The reaction was allowed to cool and the solvent was evaporated under reduced pressure. The residue was subjected to column chromatography (pure hexane) to give pure 28(131.9mg, 0.56mmol, 85%) as colorless oil.
2- (1H-indol-3-yl) ethyl 3-phenylpropionate (31)
Figure BDA0003487304920000172
Adding Ni (C) to a 12mL screw cap vial4-CF3stb)3(20.1mg, 0.02mmol, 0.1 eq.), terpyridine (4.7mg, 0.02mmol,0.1 equiv), benzyl (3-phenylpropionyl) carbamic acid tert-butyl ester (67.9mg, 0.20mmol, 1.00 equiv) and tryptophol (40.3mg, 0.25mmol, 1.25 equiv). Toluene (0.2mL) was added and the vial was placed in a pre-heated oil bath at 130 ℃. After stirring for 23h, the solution was allowed to cool to room temperature and the contents were transferred to a round bottom flask with EtOAc and hexanes. The solvent was removed under reduced pressure, and the crude residue was purified via column chromatography (7: 1; hexane/EtOAc) to provide 31(38.5mg, 0.13mmol, 65% yield) as an orange oil.
2-methylundecane (34)
Figure BDA0003487304920000181
Adding Ni (C) to a 12mL screw cap vial4-CF3stb)3(10.0mg, 0.010mmol, 0.04 eq.) and 2, 6-bis ((R) -4-phenyl-4, 5-dihydro
Figure BDA0003487304920000184
Oxazol-2-yl) pyridine (7.4mg, 0.020mmol, 0.08 eq). DMA (0.4mL) was added under argon, the dark blue solution was stirred at room temperature for 10min, and tetradecane (internal standard for GC analysis, 20 μ L, 0.077mmol) was added. The mixture was stirred at room temperature for another 10min, and n-nonylzinc bromide solution (0.85M DMA solution, 0.47mL, 0.400mmol, 1.57 equiv.) and isopropyl bromide (24 μ L, 0.256mmol, 1.00 equiv.) were added. After the reaction mixture was stirred at 60 ℃ for 20 hours, 34 was determined to be 58% yield by GC-FID analysis.
1-Vinylnaphthalene (37)
Figure BDA0003487304920000182
Adding Ni to screw cap vial4-CF3stb)3(10.1mg, 0.01mmol, 0.05 eq), a vacuum/argon cycle was performed and the vial was transferred to a glove box. Xantphos (5.8mg, 0.01mmol, 0.05 equiv.) was added and the vial was removed from the glove boxAnd (6) discharging. THF (150. mu.L), 1-naphthalene bromide (28.0. mu.L, 41.4mg, 0.2mmol) and vinyl zinc bromide (1M solution in THF/NMP, 350. mu.L, 1.75 equiv) were added. The reaction was heated to 50 ℃ for 5h and then diluted with EtOAc. A pod (25 μ L, 21.6mg) was added as an internal standard, 37 determined to be 92% yield via GC-FID analysis.
Naphthalene (40)
Figure BDA0003487304920000183
To a 12mL screw cap vial was added 2- (methylthio) naphthalene (87.2mg, 0.50mmol, 1.0 equiv.) and Ni (R) ((R))4- CF3stb)3(50.4mg, 0.05mmol, 0.1 equiv.). N-dodecane (internal standard for GC analysis, 20. mu.L, 0.09mmol), EtMe was added2SiH (0.13mL, 0.98mmol, 2.0 equiv.) and toluene (2 mL). The vial was placed in a pre-heated oil bath at 90 ℃ and kept under stirring for 14 hours. After cooling to room temperature, the mixture was diluted with EtOAc (4mL) and determined to be 40 in 91% yield via GC-FID analysis.
1, 2, 3, 4, 5-pentafluoro-6- (oct-4-en-4-yl) benzene (43)
Figure BDA0003487304920000191
Adding Ni to screw cap vial4-CF3stb)3(20.1mg, 0.02mmol, 0.1 equiv.) IMes & HCl (6.8mg, 0.02mmol, 0.1 equiv.) and anhydrous NaHMDS (3.6mg, 0.02mmol, 0.1 equiv.). Toluene (1.5mL) was added and the mixture was stirred for 5 min. 1, 2, 3, 4, 5-pentafluorobenzene (22.2. mu.L, 33.6mg, 0.2mmol) and 4-octin (44.0. mu.L, 33.1mg, 0.3mmol, 1.5 equiv) were added and the substrate was washed with toluene (0.5 mL). The reaction was stirred at room temperature for 3h and by addition of CH2Cl2To terminate. The mixture was filtered on a silica plug and evaporated to dryness. Alpha, alpha-trifluorotoluene (24.6. mu.L, 29.2mg, 0.2mmol, 1.0 equiv.) was added as an internal standard in a yield (90%) determined by19F NMR measurement.
As mentioned above, a long standing problem in the field of Ni catalysis has been solved by providing the complexes of the present invention as Ni (0) precatalyst, which mimics Ni (COD)2But has the advantages of being robust, air stable and easy to handle in open flask conditions. Here, the inventors report the synthesis and characterization of binary Ni (0) -olefin complexes, which meet all of these requirements and use Ni catalysis without the use of complex Schlenk techniques or glove boxes. Ni (0) -olefin complexes of the invention Ni (R)3Is a unique example of a modular Ni (0) -olefin complex that has significant stability in air and benefits from the high reactivity in solution brought about by its 16-electron configuration. Its catalytic ability has been expressed in terms of Ni (COD)2Have shown Ni (R)3Is an excellent precatalyst in Ni catalyzed transformations. Unlike conventional air-stable precursors based on Ni (II) complexes, Ni (R)3Is characterized by its inherent ability to deliver Ni (0) species in solution and to provide discrete and well-defined Ni (0) -ligand complexes. May expect Ni (R)3The remarkable performance as a Ni (0) precatalyst will rapidly extend to the entire Ni catalytic domain, thus enabling easy setting and acceleration of discovery of new reactivities.
(E) -pent-3-enenitrile (45)
Figure BDA0003487304920000201
This compound was prepared according to literature procedures, but with complex 6 replacing Ni (COD)2. Adding Ni (to Schlenk tube)4-tBustb)3(1.04g, 1.11mmol, 0.9 mol%) and PPh3(2.91g, 11.1mmol, 9 mol%). 2-Methylbut-3-enenitrile (12.5ml, 10.0g, 123.3mmol, 1 eq) was added and the reaction heated to 100 ℃ for 3 h. After allowing the reaction to cool to room temperature, the solution was opened to air and transferred to a round bottom flask with non-dry toluene. Distillation was attempted, but due to the product and three otherFails due to close boiling points of the isomers. The entire portion is combined with the distillation residue and CH is added2Br2(8.65mL, 21.43g, 123.3mmol, 1 equiv.) as an internal standard. The yields were determined by NMR: 67% (6.70g, 82.6 mmol).
Alpha-olefin C6-C22
Figure BDA0003487304920000202
These compounds were prepared using literature procedures, but with complex 6 replacing Ni (COD)2. A 50mL steel autoclave with a glass inlet was placed under argon. Adding Ni (to Schlenk tube)4-tBustb)3(12.2mg, 0.013mmol, 1 equiv.), 1-phenyl-2- (triphenyl-. lamda.) -5Phosphomethyleneethan-1-one (4.9mg, 0.013mmol, 1 equiv.) and PPh3(3.4mg, 0.013mmol, 1 equivalent). The solid was dissolved in toluene (20mL) and transferred to the autoclave with a syringe. The autoclave was pressurized with 5bar of ethylene gas and stirred at 25 ℃ for 15 h. The autoclave was then pressurized and heated with 60bar of ethylene to 60 ℃ for 45 min. The reaction exhibited exothermic behavior, which resulted in pressure and temperature rise, and peaked at 80bar and 75 ℃ internal temperature. The autoclave was brought to room temperature and the pressure was released. 1-undecene (200. mu.L, 150mg) was added as an internal standard and a GC sample was prepared (filtered on a silica plug, eluted with pentane).
GC analysis results:
carbon number # of Quality of mmol Required amount of turnover mmol of ethylene
6 72.0 0.856 3 2.57
8 125.1 1.115 4 4.46
10 97.1 0.692 5 3.46
12 83.4 0.495 6 2.97
14 70.8 0.361 7 2.53
16 65.5 0.292 8 2.34
18 68.1 0.270 9 2.43
20 55.0 0.196 10 1.96
22 52.9 0.171 11 1.88
Sum of 689.9 24.59
Ni(PPh3)2(4-tBustb)(48)
Figure BDA0003487304920000211
Mixing Ni (A) with4-tBustb)3(46.8mg, 0.05mmol, 1 eq.) and PPh3(52.4mg, 0.2mmol, 4 equiv.) is dissolved in d8-toluene (1mL) and transferred to NMR tube.31P NMR analysis showed 1: 1 mixture of complex 48 and 2 equivalents of free PPh3. Following the same procedure, Ni (COD)2(13.8mg, 0.05mmol, 1 eq.) and PPh3(52.4mg, 0.2mmol, 4 equiv.) is dissolved in d 8-toluene (1mL) and purified by31P NMR was analyzed. Ni (COD) (PPh)3)2And Ni (PPh)3)41 of (1): 3, and mixing the mixture.
Summarizing the above, the present invention provides the synthesis of air stable 16-electron trans-olefin-Ni (0) complexes that differ in their substituents in the aromatic ring of the supporting stilbene and their use in different catalytic applications. Systematic studies of these substituents have enabled the present inventors to establish that a source of high stability to oxidation is a consequence of the steric requirements inferred by the preference of the substituents at the para position of the stilbene ligand. This basic observation proved to be an excellent source of Ni (0) with significant physical properties. The complexes of the invention provide faster depending on their actual substitution on the aryl residueHas broader catalytic performance and has been shown to be superior to ni (cod) in challenging catalytic conversions at the same level in most applications2. Complexes of the invention with Ni (COD)2High similarity of reactivity, wide applicability, high practicality and robustness will find rapid application in the field of Ni catalysis.

Claims (11)

1. air-Stable Ni (R)3-a complex, wherein Ni represents Ni (0), and R may be the same or different, and represents a trans stilbene of formula (I):
Figure FDA0003487304910000011
wherein R is1-R10May be the same or different and is selected from H, Cl, Br, F, CN, C1-C6Alkyl or C3-C6Cycloalkyl, which alkyl or cycloalkyl may optionally be substituted with one or more halogen,
wherein R is11-R12May be the same or different, and is selected from H, C1-C6Alkyl radical, C3-C6Cycloalkyl, -O-C1-C6Alkyl or-O-C3-C6A cycloalkyl group,
provided that R is1-R12Is not hydrogen.
2. Air stable Ni (R) according to claim 13-a complex of a compound of formula (I),
wherein Ni represents Ni (0),
wherein R are the same or different and represent trans stilbene of formula (I);
wherein in formula (I), R1-R5And R6-R10Is the same or different and is selected from Cl, Br, F, CN, C1-C8Alkyl or C3-C6Cycloalkyl, the alkyl or cycloalkyl group may optionally beIs substituted with one or more halogens, and is preferably selected from C1-C8Alkyl, which may optionally be branched and/or substituted with one or more halogens, and other R1-R10Is hydrogen, and R11-R12May be the same or different, and is selected from H, C1-C8Alkyl radical, C3-C6Cycloalkyl, -O-C1-C8Alkyl or-O-C3-C6A cycloalkyl group.
3. Air stable Ni (R) according to claim 13-a complex of a compound of formula (I),
wherein Ni represents Ni (0),
wherein R are the same or different, and represents a trans stilbene of formula (I):
wherein in formula (I), R3And R8Are identical or different and are selected from C1-C8Alkyl, which may optionally be substituted with one or more halogens, and the remainder of R1-R10Is hydrogen, and R11-R12May be the same or different, and is selected from H, C1-C6Alkyl, -O-C1-C6Alkyl radical, C3-C6Cycloalkyl or-O-C3-C6A cycloalkyl group.
4. Air stable Ni (R) according to claim 13-a complex of a compound of formula (I),
wherein Ni represents Ni (0),
wherein R are the same or different, and represents a trans stilbene of formula (I):
wherein in formula (I), R3And R8Are identical or different and are selected from C1-C8Perfluoroalkyl group, and the rest of R1-R10Is hydrogen, and R11-R12May be the same or different, and is selected from H, C1-C6Alkyl, O-C1-C6Alkyl radical, C3-C6Cycloalkyl or-O-C3-C6A cycloalkyl group.
5. Air stable Ni (R) according to claim 13-a complex of a compound of formula (I),
wherein Ni represents Ni (0),
wherein R are the same, and represents a trans stilbene of formula (I):
wherein in formula (I), R3And R8Each is C1-C8Perfluoroalkyl, and other R1-R10And R11-R12Is hydrogen.
6. Air stable Ni (R) according to claim 13-a complex of a compound of formula (I),
wherein Ni represents Ni (0),
wherein R are the same, and represents a trans stilbene of formula (I):
wherein in formula (I), R3And R8Each is-CF3And other R1-R10And R11-R12Is hydrogen.
7. Preparation of air-Stable Ni (R)3-a complex, wherein Ni represents Ni (0) and R may be the same or different, and represents a trans stilbene of formula (I):
Figure FDA0003487304910000031
wherein R is1-R10May be the same or different and is selected from H, Cl, Br, F, CN, C1-C6Alkyl or C3-C6Cycloalkyl, which alkyl or cycloalkyl may optionally be substituted with one or more halogen,
wherein R is11-R12May be the same or different, and is selected from H, C1-C6Alkyl radical, C3-C6Cycloalkyl, -O-C1-C6Alkyl or-O-C3-C6A cycloalkyl group,
wherein is selected from NiF2、NiCl2、NiBr2、NiI2、Ni(OTf)2、Ni(BF4)2、Ni(OTs)2Ni (glyme) Cl2Ni (glyme) Br2Ni (diglyme) Cl2Ni (diglyme) Br2、Ni(NO3)2、Ni(OR13)2(wherein R is13represents-C (O) -C1-C6Alkyl, optionally substituted with one or more halogens, preferably Cl or F, (acetyl acetonate)2Ni、Ni(Ac)2Or mixtures thereof, in the presence of a nickel (II) compound of the formula Al (R)14)3With trans stilbene of the formula (I), preferably at least 3 equivalents, in the presence of an aluminum alkyl, preferably at least 2 equivalents, in which R14May be the same or different, and is selected from C1-C6Alkyl or C3-C6A cycloalkyl group.
8. Preparation of air-Stable Ni (R) according to claim 73A process for the preparation of a complex, wherein Al (R) is14)3The aluminum alkyl is selected from Al (CH)3)3Or Al (C)2H5)3。
9. Preparation of air-stabilized Ni (R) according to claim 7 or 83-a process for the preparation of a complex wherein R represents trans stilbene of formula (I) as defined in any one of claims 2 to 6.
10. Air stable Ni (R) according to any one of claims 1 to 63-use of a complex as a catalyst or pre-catalyst in organic synthesis, wherein:
ni represents Ni (0), and R may be the same or different, and represents a trans stilbene of formula (I):
Figure FDA0003487304910000041
R1-R10can be a phaseSame or different and is selected from H, Cl, Br, F, CN, C1-C6Alkyl or C3-C6Cycloalkyl, which may optionally be substituted with one or more halogen,
R11-R12may be the same or different and is selected from H, -O-C1-C6Alkyl radical, C1-C6Alkyl or C3-C6A cycloalkyl group,
optionally, provided that R1-R12Is not hydrogen.
11. Air stable Ni (R) according to any one of claims 1 to 63-use of the complex as a catalyst in organic synthesis.
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